The development of porous well-defined hybrid materials (e.g., metal-organic frameworks or MOFs) will add a new dimension to a wide number of applications ranging from supercapacitors and electrodes to "smart" membranes and thermoelectrics. From this perspective, the understanding and tailoring of the electronic properties of MOFs are key fundamental challenges that could unlock the full potential of these materials. In this work, we focused on the fundamental insights responsible for the electronic properties of three distinct classes of bimetallic systems, MM'-MOFs, MM'-MOFs, and M(ligand-M')-MOFs, in which the second metal (M') incorporation occurs through (i) metal (M) replacement in the framework nodes (type I), (ii) metal node extension (type II), and (iii) metal coordination to the organic ligand (type III), respectively. We employed microwave conductivity, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, powder X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, pressed-pellet conductivity, and theoretical modeling to shed light on the key factors responsible for the tunability of MOF electronic structures. Experimental prescreening of MOFs was performed based on changes in the density of electronic states near the Fermi edge, which was used as a starting point for further selection of suitable MOFs. As a result, we demonstrated that the tailoring of MOF electronic properties could be performed as a function of metal node engineering, framework topology, and/or the presence of unsaturated metal sites while preserving framework porosity and structural integrity. These studies unveil the possible pathways for transforming the electronic properties of MOFs from insulating to semiconducting, as well as provide a blueprint for the development of hybrid porous materials with desirable electronic structures.

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A simple, noninvasive method using Raman spectroscopy for the estimation of the thickness of graphene layers grown epitaxially on silicon carbide (SiC) is presented, enabling simultaneous determination of thickness, grain size, and disorder using the spectra. The attenuation of the substrate Raman signal due to the graphene overlayer is found to be dependent on the graphene film thickness deduced from x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) of the surfaces. We explain this dependence using an absorbing overlayer model. This method can be used for mapping graphene thickness over a region and is capable of estimating thickness of multilayer graphene films beyond that possible by XPS and Auger electron spectroscopy (AES).

A betavoltaic cell in 4H SiC is demonstrated. A p-n diode structure was used to collect the charge from a 1mCi Ni-63 source. An open circuit voltage of 0.72V and a short circuit current density of 16.8nA∕cm2 were measured in a single p-n junction. A 6% lower bound on the power conversion efficiency was obtained. A simple photovoltaic-type model was used to explain the results. Fill factor and backscattering effects were included in the efficiency calculation. The performance of the device was limited by edge recombination.

We report on the fabrication of gallium nitride (GaN) nanowire field-effect transistors (FETs) with both bottom-gate and top-gate structures, with very high yield using a unique pre-alignment process. The catalyst positions were chosen to be aligned with the source/drain position, and Ni catalysts with a diameter of 200 nm were deposited selectively at these pre-determined positions. Electrostatic analysis was performed for the bottom-gate devices to estimate the nanowire’s electrical characteristics. Comparison of the bottom-gate and the top-gate structures indicated that better performance, in terms of saturation and breakdown characteristics, can be obtained using the top-gate structure. For the top-gate nanowire FETs, temperature-dependent characteristics were investigated up to the current saturation regime, and memory effects were observed at room temperature.

Tetrafluorosilane (SiF4) gas precursor is utilized to eliminate Si gas phase nucleation and Si parasitic deposition during silicon carbide (SiC) epitaxial growth, otherwise unachievable in similar growth conditions using conventional silane (SiH4) and dichlorosilane (SiCl2H2/DCS) precursors. Higher SiF bond strength (565 kJ mol−1) in SiF4 prevents early gas decomposition and Si cluster formation, essential for high temperature SiC chemical vapor deposition (CVD), and yet enables growth of high quality epitaxy in an improved particulate suppressed growth condition. High quality, thick 4H‐SiC epilayers >100 µm have been demonstrated using SiF4 with excellent surface morphology, polytype uniformity, crystallinity and low defect density. Significant (80%) suppression of parasitic deposition (left) using SiF4 reduces particulate generation during growth, and improves the epilayer quality (right).

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We present epitaxial graphene (EG) growth on nonpolar 6H-SiC-faces by solid-state decomposition of the SiC substrate in the Knudsen flow regime in vacuum. The material characteristics are compared with those known for EG grown on polar SiC-faces under similar growth conditions. X-ray photoelectron spectroscopy (XPS) measurements indicate that nonpolar faces have thicker layers than polar faces. Among nonpolar faces, the m-plane (11̅ 00) has thicker layers than the aplane (112̅ 0). Atomic force microscopy (AFM) shows nanocrystalline graphite features for nonpolar faces, consistent with the small grain size measured by Raman spectroscopy. This is attributed to the lack of a hexagonal template, unlike on the polar Si-and C-faces. These nonpolar face EG films exhibited stress decreasing with increasing growth temperature. These variations are interpreted on the basis of different growth mechanisms on the various faces, as expected from the large differences in surface energy and step dynamics on the various SiC surfaces. Surfaces with smaller grain sizes systematically exhibited thicker layers. Using this observation, we argue that multilayer EG growth, after the nucleation of the first layers, is determined primarily by Si diffusion through grain boundaries and defects, as Si cannot diffuse through a perfect graphene lattice. A greater density of grain boundaries allows more Si to escape during growth, allowing thicker layers of carbon to be grown.